JP2008163314A - Polypropylene glycol divinyl ether - Google Patents
Polypropylene glycol divinyl ether Download PDFInfo
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本発明は、新規なビニルエーテル並びにその製造方法及び用途に関し、更に詳しくは例えば、電子材料に用いられる低臭気、低揮発性且つ、低皮膚刺激性であって、毒性が低く、硬化性、密着性、耐水性に優れる重合組成物原料として、極めて有用なポリプロピレングリコールジビニルエーテルに関する。 The present invention relates to a novel vinyl ether and a method for producing the same, and more particularly, for example, low odor, low volatility and low skin irritation used for electronic materials, low toxicity, curability, and adhesion. The present invention relates to a polypropylene glycol divinyl ether that is extremely useful as a raw material for a polymerization composition having excellent water resistance.
本発明に係るポリプロピレングリコールジビニルエーテルに関しては、ケミカルアブストラクト（Chemical Abstract）に記載がなく、また、本発明者等の知るかぎりでは、その他の文献にも記載が見当たらないので、この化合物は新規化合物であると考えられる。 Regarding the polypropylene glycol divinyl ether according to the present invention, there is no description in the chemical abstract (Chemical Abstract), and as far as the present inventors know, there is no description in other literatures. It is believed that there is.
本発明の目的は、ポリプロピレングリコールジビニルエーテル並びにその製造方法及び用途を提供することにある。 An object of the present invention is to provide polypropylene glycol divinyl ether and a production method and use thereof.
本発明に従えば、式（Ｉ）：
（式中、ｎは２〜７０の整数を表す）
で表されるビニルエーテルが提供される。
According to the invention, the formula (I):
(In the formula, n represents an integer of 2 to 70)
The vinyl ether represented by these is provided.
本発明に係るポリプロピレングリコールジビニルエーテルは、低臭気、低揮発性且つ、低皮膚刺激性であって、毒性が低く、また、硬化性、密着性、耐水性に優れる重合組成物原料として、極めて有用である。 The polypropylene glycol divinyl ether according to the present invention is extremely useful as a raw material for a polymer composition having low odor, low volatility, low skin irritation, low toxicity, and excellent curability, adhesion, and water resistance. It is.
また、反応性を有するビニルエーテル基を２つ持つだけでなく、長い親水性と疎水性の骨格を分子内に併せ持ち、なおかつ、安価で工業的に入手容易な原料を用いて調製可能であり、原料の分子量を適切に選ぶことにより、その物性を自由に変えられる利点がある。
さらに、本発明での分子量の範囲では、常温においては液状であり、ハンドリングがし易く、各種資材との相溶性が高く、水に対する適度な溶解性を示す一方で、公知であるポリエチレングリコールジビニルエーテルに比べ、低吸湿性で保管時の品質管理が容易等の特徴があり、その欠点を解消できる。
In addition to having two reactive vinyl ether groups, it has a long hydrophilic and hydrophobic skeleton in the molecule, and can be prepared using inexpensive and industrially available raw materials. By properly selecting the molecular weight, there is an advantage that the physical properties can be freely changed.
Furthermore, within the range of molecular weight in the present invention, it is liquid at normal temperature, is easy to handle, has high compatibility with various materials, and exhibits moderate solubility in water, while being known polyethylene glycol divinyl ether. Compared to the above, it has low hygroscopicity and easy quality control during storage, and the disadvantages can be solved.
製法に関しては、本発明によれば、アルカリ触媒を用いるにも関わらず、穏和な条件を採用することにより、主鎖の断絶を起こすことなく、純度の高い目的の化合物を調製できる。
Regarding the production method, according to the present invention, the target compound with high purity can be prepared by adopting mild conditions without causing breakage of the main chain, despite using an alkali catalyst.
以下、本発明について詳しく説明する。
本発明に係るビニルエーテル（Ｉ）は、次のような反応式に従って調製することができる。
本発明化合物の具体的な合成法としては、例えば、次のような方法を挙げることができる。
The present invention will be described in detail below.
The vinyl ether (I) according to the present invention can be prepared according to the following reaction formula.
Specific examples of the method for synthesizing the compound of the present invention include the following methods.
例えば、ＳＵＳ（ステンレス鋼）製の耐圧反応容器中に、ポリプロピレングリコールを入れ、反応触媒として、例えば、水酸化カリウム、水酸化ナトリウム等のアルカリ金属水酸化物などのアルカリ性化合物を添加する。
アルカリ性化合物の添加量としてはポリプロピレングリコール１．００モルに対して約０．０２〜０．４０ミリモルで行うのが好ましく、０．１０〜０．３０モルがより好ましい。次いで、窒素ガスにより該容器内を置換した後、反応容器を密封して、アセチレンを圧入しながら、昇温して反応させと、本発明の新規化合物であるプロピレングリコールジビニルエーテルが生成する。
反応条件としては、アセチレンの圧力が０．０１〜０．１８ＭＰａで１１０〜１４０℃が好ましい。より好ましくは０．１５〜０．１８ＭＰａで１２０〜１３０℃である。
For example, polypropylene glycol is placed in a pressure resistant reaction vessel made of SUS (stainless steel), and an alkaline compound such as an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide is added as a reaction catalyst.
The addition amount of the alkaline compound is preferably about 0.02 to 0.40 mmol, more preferably 0.10 to 0.30 mol, relative to 1.00 mol of polypropylene glycol. Next, after the inside of the container is replaced with nitrogen gas, the reaction container is sealed, and the reaction is carried out by raising the temperature while injecting acetylene, whereby propylene glycol divinyl ether, which is a novel compound of the present invention, is produced.
The reaction conditions are preferably acetylene pressure of 0.01 to 0.18 MPa and 110 to 140 ° C. More preferably, it is 120-130 degreeC at 0.15-0.18 MPa.
さらに、反応後は、残存する触媒と未反応原料、及び反応中間体や副生成物等を除去するため水洗した後、有機溶剤による稀釈、乾燥することが好ましい。
稀釈のための有機溶剤の具体例としては、塩化メチレン、クロロホルム、ベンゼン、トルエン、キシレン、酢酸メチル、酢酸エチル等が使用できるが、効率の良さから、酢酸エチルが好ましい。
Further, after the reaction, it is preferable to wash with water to remove the remaining catalyst, unreacted raw materials, reaction intermediates and by-products, and then dilute with an organic solvent and dry.
Specific examples of the organic solvent for dilution can include methylene chloride, chloroform, benzene, toluene, xylene, methyl acetate, ethyl acetate, and the like, but ethyl acetate is preferable from the viewpoint of efficiency.
一方、脱水処理のための乾燥剤の具体例としては、硫酸マグネシウム、硫酸ナトリウム、塩化カルシウム等の無水無機塩が使用できるが、脱水の効率や本抽出液に対する溶解性の低さを考慮した品質上の面から、無水無機塩が望ましく、特に硫酸マグネシウムが好適に使用できる。
On the other hand, as specific examples of desiccants for dehydration treatment, anhydrous inorganic salts such as magnesium sulfate, sodium sulfate, calcium chloride, etc. can be used, but quality considering the efficiency of dehydration and low solubility in this extract. In view of the above, anhydrous inorganic salts are desirable, and magnesium sulfate can be particularly preferably used.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例１
攪拌機、圧力ゲージ、温度計、瓦斯導入管、ガスパージラインを備えた２０００ｍｌのＳＵＳ製耐圧反応容器に、ポリプロピレングリコールジオール（重量平均分子量１０００）４２０．７ｇを仕込み、触媒として純度９５重量％の水酸化カリウム４．２ｇ（約０．０７モル）を添加した。攪拌しながら窒素ガスを流して該容器内を窒素置換した後、反応容器を密封し、容器内にアセチレンガスを約０．１８ＭＰａの圧力で圧入した。次いで、ゲージ圧力を約０．１８ＭＰａに保ちながら反応容器内温が１２０℃になるまで昇温し、反応温度が１２０℃に達してから、１３時間反応させた。この間、逐次アセチレンガスを補充して反応容器内の圧力は常に約０．１８ＭＰａに保った。
反応終了後、残留するアセチレンガスをパージして反応液４４５．０ｇを得た。次いで、反応液を水洗した後、酢酸エチルで稀釈、乾燥剤として無水硫酸マグネシウムを加えた。乾燥剤を濾過後、減圧下に反応液を濃縮して、ポリプロピレングリコールジビニルエーテル３６７．８ｇを得た。
高速液体クロマトグラフィー（ＧＰＣ）分析の結果、該ポリプロピレングリコールジビニルエーテルの重量平均分子量（Ｍw）は約１１００、数平均分子量（Ｍn）は約１０００、分子量分布（重量平均分子量Ｍw／数平均分子量Ｍn）は１．１０であった。
また、ＮＭＲ解析から算出した該ポリプロピレングリコールジビニルエーテルの平均分子量は約１２００であった。
得られたポリプロピレングリコールジビニルエーテルのＮＭＲの測定結果は次のとおりである。
１ＨＮＭＲ（ＣＤＣｌ３、６０ＭＨz）：δｐｐｍ
０．７−１．６（ｍ，５５Ｈ，−ＣＨ３）
３．０−４．４（ｍ，６５Ｈ，−ＣＨ and −ＣＨ２ and
−ＣＨ＝ＣＨ ２）
６．２−６．３（ｂｒ ｄ，Ｊ＝６．６Ｈｚ，１Ｈ，―ＣＨ−ＣＨ２）
６．４−６．６（ｂｒ ｄ，Ｊ＝６．３Ｈｚ，１Ｈ，―ＣＨ＝ＣＨ２）
Example 1
A 2000 ml SUS pressure-resistant reaction vessel equipped with a stirrer, a pressure gauge, a thermometer, a gas introduction line, and a gas purge line was charged with 420.7 g of polypropylene glycol diol (weight average molecular weight 1000), and a hydroxide having a purity of 95% by weight as a catalyst. 4.2 g (about 0.07 mol) of potassium was added. Nitrogen gas was allowed to flow while stirring to replace the inside of the vessel with nitrogen, and then the reaction vessel was sealed, and acetylene gas was injected into the vessel at a pressure of about 0.18 MPa. Next, while maintaining the gauge pressure at about 0.18 MPa, the temperature inside the reaction vessel was raised to 120 ° C., and the reaction was carried out for 13 hours after the reaction temperature reached 120 ° C. During this time, acetylene gas was successively replenished, and the pressure in the reaction vessel was always kept at about 0.18 MPa.
After the reaction was completed, the remaining acetylene gas was purged to obtain 445.0 g of a reaction solution. Next, the reaction solution was washed with water, diluted with ethyl acetate, and anhydrous magnesium sulfate was added as a drying agent. After filtering the desiccant, the reaction solution was concentrated under reduced pressure to obtain 367.8 g of polypropylene glycol divinyl ether.
As a result of high performance liquid chromatography (GPC) analysis, the polypropylene glycol divinyl ether has a weight average molecular weight (Mw) of about 1100, a number average molecular weight (Mn) of about 1000, and a molecular weight distribution (weight average molecular weight Mw / number average molecular weight Mn). Was 1.10.
The average molecular weight of the polypropylene glycol divinyl ether calculated from NMR analysis was about 1200.
The NMR measurement results of the resulting polypropylene glycol divinyl ether are as follows.
1 HNMR (CDCl 3 , 60 MHz): δ ppm
0.7-1.6 (m, 55H, -CH 3 )
3.0-4.4 (m, 65H, -CH and -CH 2 and
-CH = C H 2)
6.2-6.3 (br d, J = 6.6Hz , 1H, -C H -CH 2)
6.4-6.6 (br d, J = 6.3 Hz, 1H, -C H = CH 2 )
実施例２
攪拌機、圧力ゲージ、温度計、瓦斯導入管、ガスパージラインを備えた２０００ｍｌのＳＵＳ製耐圧反応容器に、ポリプロピレングリコールジオール（重量平均分子量２０００）４２０．１ｇを仕込み、触媒として純度９５重量％の水酸化カリウム３．２ｇ（約０．０５モル）を添加した。攪拌しながら窒素ガスを流して該容器内を窒素置換した後、反応容器を密封し、容器内にアセチレンガスを約０．１８ＭＰａの圧力で圧入した。次いで、ゲージ圧力を約０．１８ＭＰａに保ちながら反応容器内温が１２０℃になるまで昇温し、反応温度が１２０℃に達してから、約６時間１０分反応させた。この間、逐次アセチレンガスを補充して反応容器内の圧力は常に約０．１８ＭＰａに保った。
反応終了後、残留するアセチレンガスをパージして反応液４３０．９ｇを得た。次いで、反応液を水洗した後、酢酸エチルで稀釈、乾燥剤として無水硫酸マグネシウムを加えた。乾燥剤を濾過後、減圧下に反応液を濃縮して、ポリプロピレングリコールジビニルエーテル３２６．０ｇを得た。
ＧＰＣ分析の結果、該ポリプロピレングリコールジビニルエーテルの重量平均分子量（Ｍw）は約２２００、数平均分子量（Ｍn）は約２１００、分子量分布は１．０４であった。
また、ＮＭＲ解析から算出した該ポリプロピレングリコールジビニルエーテルの平均分子量は約２１００であった。
得られたポリプロピレングリコールジビニルエーテルのＮＭＲの測定結果は次のとおりである。
１ＨＮＭＲ（ＣＤＣｌ３、６０ＭＨz）：δｐｐｍ
０．７−１．５（ｍ，１０４Ｈ，−ＣＨ３）
３．２−４．４（ｍ，１１５Ｈ，−ＣＨ and −ＣＨ２
and −ＣＨ＝ＣＨ ２）
６．２−６．３（ｂｒ ｄ，Ｊ＝６．６Ｈｚ，１Ｈ，―ＣＨ＝ＣＨ２）
６．４−６．６（ｂｒ ｄ，Ｊ＝６．６Ｈｚ，１Ｈ，―ＣＨ＝ＣＨ２）
Example 2
A 2000 ml SUS pressure-resistant reaction vessel equipped with a stirrer, a pressure gauge, a thermometer, a gas introduction line, and a gas purge line was charged with 420.1 g of polypropylene glycol diol (weight average molecular weight 2000), and a hydroxide having a purity of 95% by weight as a catalyst. Potassium 3.2 g (about 0.05 mol) was added. Nitrogen gas was allowed to flow while stirring to replace the inside of the vessel with nitrogen, and then the reaction vessel was sealed, and acetylene gas was injected into the vessel at a pressure of about 0.18 MPa. Next, while maintaining the gauge pressure at about 0.18 MPa, the temperature inside the reaction vessel was raised to 120 ° C., and after the reaction temperature reached 120 ° C., the reaction was carried out for about 6 hours and 10 minutes. During this time, acetylene gas was successively replenished, and the pressure in the reaction vessel was always kept at about 0.18 MPa.
After the reaction was completed, the remaining acetylene gas was purged to obtain 430.9 g of a reaction solution. Next, the reaction solution was washed with water, diluted with ethyl acetate, and anhydrous magnesium sulfate was added as a drying agent. After filtering the desiccant, the reaction solution was concentrated under reduced pressure to obtain 326.0 g of polypropylene glycol divinyl ether.
As a result of GPC analysis, the polypropylene glycol divinyl ether had a weight average molecular weight (Mw) of about 2200, a number average molecular weight (Mn) of about 2100, and a molecular weight distribution of 1.04.
The average molecular weight of the polypropylene glycol divinyl ether calculated from NMR analysis was about 2100.
The NMR measurement results of the resulting polypropylene glycol divinyl ether are as follows.
1 HNMR (CDCl 3 , 60 MHz): δ ppm
0.7-1.5 (m, 104H, -CH 3 )
3.2-4.4 (m, 115H, -CH and -CH 2
and -CH = C H 2 )
6.2-6.3 (br d, J = 6.6 Hz, 1H, -C H = CH 2 )
6.4-6.6 (br d, J = 6.6 Hz, 1H, -C H = CH 2 )
実施例３
攪拌機、圧力ゲージ、温度計、瓦斯導入管、ガスパージラインを備えた２０００ｍｌのＳＵＳ製耐圧反応容器に、ポリプロピレングリコールジオール（重量平均分子量３０００）４２０．４ｇを仕込み、触媒として純度９５重量％の水酸化カリウム２．３ｇ（約０．０４モル）を添加した。攪拌しながら窒素ガスを流して該容器内を窒素置換した後、反応容器を密封し、容器内にアセチレンガスを約０．１８ＭＰａの圧力で圧入した。次いで、ゲージ圧力を約０．１８ＭＰａに保ちながら反応容器内温が１２０℃になるまで昇温し、反応温度が１２０℃に達してから、約５時間３０分反応させた。この間、逐次アセチレンガスを補充して反応容器内の圧力は常に約０．１８ＭＰａに保った。
反応終了後、残留するアセチレンガスをパージして反応液４２７．２ｇを得た。次いで、反応液を水洗した後、酢酸エチルで稀釈、乾燥剤として無水硫酸マグネシウムを加えた。乾燥剤を濾過後、減圧下に反応液を濃縮して、ポリプロピレングリコールジビニルエーテル２６４．８ｇを得た。
ＧＰＣ分析の結果、該ポリプロピレングリコールジビニルエーテルの重量平均分子量（Ｍw）は約３０００、数平均分子量（Ｍn）は約２８００、分子量分布は１．０６であった。
また、ＮＭＲ解析から算出した該ポリプロピレングリコールジビニルエーテルの平均分子量は約３９００であった。
得られたポリプロピレングリコールジビニルエーテルのＮＭＲの測定結果は次のとおりである。
１ＨＮＭＲ（ＣＤＣｌ３、６０ＭＨz）：δｐｐｍ
０．８−１．９（ｍ，１９４Ｈ，−ＣＨ３）
３．２−４．４（ｍ，２０９Ｈ，−ＣＨ and −ＣＨ２
and −ＣＨ＝ＣＨ ２）
６．２−６．３（ｂｒ ｄ，Ｊ＝６．５Ｈｚ，１Ｈ，―ＣＨ＝ＣＨ２）
６．４−６．６（ｂｒ ｄ，Ｊ＝６．２Ｈｚ，１Ｈ，―ＣＨ＝ＣＨ２）
Example 3
A 2000 ml SUS pressure-resistant reaction vessel equipped with a stirrer, a pressure gauge, a thermometer, a gas introduction line, and a gas purge line was charged with 420.4 g of polypropylene glycol diol (weight average molecular weight 3000) and hydroxylated with a purity of 95% by weight as a catalyst. 2.3 g (about 0.04 mol) of potassium was added. Nitrogen gas was allowed to flow while stirring to replace the inside of the vessel with nitrogen, and then the reaction vessel was sealed, and acetylene gas was injected into the vessel at a pressure of about 0.18 MPa. Next, while maintaining the gauge pressure at about 0.18 MPa, the temperature inside the reaction vessel was raised to 120 ° C., and after the reaction temperature reached 120 ° C., the reaction was carried out for about 5 hours and 30 minutes. During this time, acetylene gas was successively replenished, and the pressure in the reaction vessel was always kept at about 0.18 MPa.
After completion of the reaction, the remaining acetylene gas was purged to obtain 427.2 g of a reaction solution. Next, the reaction solution was washed with water, diluted with ethyl acetate, and anhydrous magnesium sulfate was added as a drying agent. After filtering the desiccant, the reaction solution was concentrated under reduced pressure to obtain 264.8 g of polypropylene glycol divinyl ether.
As a result of GPC analysis, the polypropylene glycol divinyl ether had a weight average molecular weight (Mw) of about 3000, a number average molecular weight (Mn) of about 2800, and a molecular weight distribution of 1.06.
The average molecular weight of the polypropylene glycol divinyl ether calculated from NMR analysis was about 3900.
The NMR measurement results of the resulting polypropylene glycol divinyl ether are as follows.
1 HNMR (CDCl 3 , 60 MHz): δ ppm
0.8-1.9 (m, 194H, -CH 3 )
3.2-4.4 (m, 209H, -CH and -CH 2
and -CH = C H 2 )
6.2-6.3 (br d, J = 6.5 Hz, 1H, -C H = CH 2 )
6.4-6.6 (br d, J = 6.2 Hz, 1H, -C H = CH 2 )
本発明の新規化合物ポリプロピレングリコールジビニルエーテルは、低臭気、低揮発性且つ、低皮膚刺激性であって、毒性が低く、また、硬化性、密着性、耐水性に優れる重合組成物原料として、有用な特性を有することが期待できる。 The novel compound polypropylene glycol divinyl ether of the present invention has a low odor, low volatility, low skin irritation, low toxicity, and is useful as a raw material for a polymerization composition having excellent curability, adhesion and water resistance. It can be expected to have excellent characteristics.
Claims (5)
式（Ｉ）：
（式中、ｎは２〜７０の整数を表す）
で表される化合物。
Formula (I):
(In the formula, n represents an integer of 2 to 70)
A compound represented by
式（ＩＩ）：
で表される化合物を、アルカリ金属化合物存在下に、アセチレンと反応させてなる請求項１に記載の化合物。
Formula (II):
The compound of Claim 1 formed by making the compound represented by these react with acetylene in presence of an alkali metal compound.
The raw material for electronic materials using the compound of Claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007297588A JP2008163314A (en) | 2006-12-07 | 2007-11-16 | Polypropylene glycol divinyl ether |
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| JPH03505593A (en) * | 1988-02-29 | 1991-12-05 | ジーエイエフ ケミカルズ コーポレーション | Solvent resistant radiation curable coating |
| JPH0873272A (en) * | 1994-06-29 | 1996-03-19 | Kyocera Corp | Ceramic molding composition |
| JPH08133844A (en) * | 1994-10-31 | 1996-05-28 | Kyocera Corp | Composition for forming ceramics |
| JPH08225479A (en) * | 1994-10-29 | 1996-09-03 | Basf Ag | Method of preparing monovinyl ether |
| JP2003261673A (en) * | 2002-03-12 | 2003-09-19 | Dainippon Ink & Chem Inc | Ultraviolet curable composition |
| JP2005105044A (en) * | 2003-09-29 | 2005-04-21 | Dainippon Ink & Chem Inc | Curable resin composition, method for curing and cured product |
| JP2005290324A (en) * | 2004-04-05 | 2005-10-20 | Sumika Bayer Urethane Kk | Low-hardness thermosetting polyurethane elastomer and method for producing the same |
| JP2006083394A (en) * | 2003-05-08 | 2006-03-30 | Nishikawa Rubber Co Ltd | Biodegradable resin molded article |
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| JPS4925249B1 (en) * | 1969-10-14 | 1974-06-28 | ||
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| JPH03505593A (en) * | 1988-02-29 | 1991-12-05 | ジーエイエフ ケミカルズ コーポレーション | Solvent resistant radiation curable coating |
| JPH0873272A (en) * | 1994-06-29 | 1996-03-19 | Kyocera Corp | Ceramic molding composition |
| JPH08225479A (en) * | 1994-10-29 | 1996-09-03 | Basf Ag | Method of preparing monovinyl ether |
| JPH08133844A (en) * | 1994-10-31 | 1996-05-28 | Kyocera Corp | Composition for forming ceramics |
| JP2003261673A (en) * | 2002-03-12 | 2003-09-19 | Dainippon Ink & Chem Inc | Ultraviolet curable composition |
| JP2006083394A (en) * | 2003-05-08 | 2006-03-30 | Nishikawa Rubber Co Ltd | Biodegradable resin molded article |
| JP2005105044A (en) * | 2003-09-29 | 2005-04-21 | Dainippon Ink & Chem Inc | Curable resin composition, method for curing and cured product |
| JP2005290324A (en) * | 2004-04-05 | 2005-10-20 | Sumika Bayer Urethane Kk | Low-hardness thermosetting polyurethane elastomer and method for producing the same |
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